DOCSLIB.ORG

Download Article

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Download Article 6th International Conference on Mechatronics, Materials, Biotechnology and Environment (ICMMBE 2016) The investigation of direct C-glycosylation of monosaccharides under microwave activation Nan Cao College of Chemistry Chemical Engineering and Material Science, Zaozhuang University, China [email protected] Keywords: C-glycoside; glucose; microwave; direct C-glycosylation Abstract Carbohydrates are a class of important compounds widely occurring in nature and are the main energy source required for all living organisms. Based on the variation of glycosidic bonds in carbohydrates, they can be divided into O-glycosides, C-glycosides, thioglycosides, and other types, among which C-glycoside is an important glycoside. Research reports on C-glycosylation have noted many challenges, such as tedious steps for the synthesis of glycosyl donors, the narrow application scope of the reaction, and the low efficiency of glycosylation. In the present paper, microwaves were used to activate the direct C-glycosylation of monosaccharides. By optimizing reaction conditions, improving reaction efficiency, and investigating reaction mechanisms, we aimed to obtain an ideal C-glycosylation method. Introduction Along with proteins and DNA, carbohydrates are important biomacromolecules. Carbohydrate chemistry plays an extremely important role in life science and pharmaceutical research[1-4]. Based on the variation of glycosidic bonds in carbohydrates, they can be divided into O-glycosides, C-glycosides, thioglycosides, and other types, among which C-glycoside is an important glycoside. When oxygen in the O-glycosidic bond is replaced with carbon, the resulting compound is referred to as a C-glycoside[5]. Research reports of C-glycosylation have noted many challenges, such as tedious steps for the synthesis of glycosyl donors, the narrow scope of application for the reaction, and the low efficiency of glycosylation.[6] In the present paper, microwaves were used to activate the direct C-glycosylation of monosaccharides. By optimizing reaction conditions, improving reaction efficiency, and investigating reaction mechanisms, we aimed to obtain an ideal C-glycosylation method. Experiment Distillation purification of acetylacetone. A total of 20 ml of acetylacetone was added to a rounded-bottom flask, and a general distillation apparatus was conFig.d. Under magnetic stirring, acetylacetone was heated and distilled; the fraction at 140-142°C was collected and stored for use. 4.00 g (22.2 mmol) of glucose, 7.40 g (88.8 mmol) of sodium bicarbonate, 10 ml of tetrahydrofuran, 20 ml of water, and 4.6 ml (44 mmol) of newly distilled acetylacetone were added to a flask to perform the reaction. When the color of the reaction solution turned to light yellow, a condenser was connected to the flask. The setup was then placed in a microwave reactor at a temperature of 75°C and a power of 300 W; the reaction lasted for 30 min under magnetic stirring and heating reflux. A 10% methanolic sulfuric acid solution was prepared and used as the chromogenic reagent. Methanol/ethyl acetate (1/6) solution was prepared and used as the developer for thin-layer chromatography (TLC). The thin-layer chromatogram is shown in Fig. 1; spot 1 corresponds to the reaction mixture and spot 2 to glucose. The TLC results indicate that glucose reacted completely. © 2016. The authors - Published by Atlantis Press 608 Fig. 1(left) Thin-layer chromatograms after 30 min. Fig. 2(right) Thin-layer chromatograms of reaction mixture. Fig. 3(left) Thin-layer chromatograms of the first 15 test tubes. Fig. 4(middle) Thin-layer chromatograms of tailing from column chromatography. Fig. 5(right) Thin-layer chromatograms after reaction for 4 hours. Tetrahydrofuran was removed by rotary evaporation, and 20 ml of ethyl acetate was then added for liquid separation. After the addition of water, the insoluble solid was returned to the flask; the solution was heated to 75°C by using a microwave reactor with a power of 300 W for 30 min. This solution was gradually heated to 90°C and reacted for 3 hours and finally heated to 100°C and reacted for 2 hours[7]. The reaction mixture was mixed with the lower phase obtained from liquid separation; the resulting mixture was concentrated by freezing. Then, 100 ml of methanol/ethyl acetate (1/1) was then added to the concentrate, and the residual salt was removed by filtration. The TLC is shown in Fig. 2, in which spot 1, spot 2, and spot 3 correspond to the reaction mixture, glucose, and acetylacetone, respectively. The TLC results indicate a complete reaction. Silica gel was added to the reaction mixture for adsorption, and the resulting solution was then spin-dried. Methanol/ethyl acetate (1/6) solution was used as the eluting agent for silica gel column chromatography. Test tubes were used to collect eluents for TLC test; the thin-layer chromatograms of the first 15 test tubes are shown in Fig. 3, where the number corresponds to the numbering of the test tubes. A sample spot started to appear from test tube 7, and pure sample appeared from test tube 15. TLC was performed in conjunction with column chromatography. Tailing in TLC appeared from test tube 82, and the sample spot disappeared from test tube 83. The TLC is shown in Fig. 4; 80, 81, 82, and 83 are the numbering of the test tubes. Spot A corresponds to the reaction mixture before column chromatography and spot B to glucose. The Fig. shows that elution was completed. The liquid of test tubes 7 to 14 was collected, evaporated by rotovap, and concentrated; the resulting concentrate was labeled as sample I. Similarly, the liquid of test tubes 15 to 81 was collected, evaporated by rotovap, and concentrated; the resulting concentrate was labeled as sample II. Ethanol was used to re-crystallize samples I and II, and activated carbon was added to adsorb its color. Rotary evaporation was used to recrystallize and spin-dry samples I and II. The resulting samples were dried 609 in a vacuum oven for 12 hours to obtain a colorless syrup-like material. The samples were weighed at 0.5021 g for sample I and 3.1669 g for sample II; the total mass was 3.6690 g. The above steps were repeated using different reaction conditions to optimize the process. The C-glycosylation was repeated: 10 g of the reaction mixture before column chromatography, 50 ml of acetic anhydride, and 10 g of sodium acetate were added to flask, magnetically stirred, and heat refluxed; the temperature was 80°C, and the reaction lasted for 4 hours. TLC was performed for the reaction mixture, and the results are shown in Fig. 5; spot 1 corresponds to pure C-glycoside and spot 2 to acetylated mixture compounds. The Fig. shows that the reaction went to completion. The reaction mixture was poured into an ice and water mixture for washing while it was still hot. The solution was stirred using a glass rod for approximately 30 min and filtered. Water washing and filtration were repeated twice. Ethanol (50%) was used for heat refluxing for 1 hour. The resulting solution was recrystallized, activated carbon was added to adsorb color, and the solution was filtered while still hot. The heat reflux was repeated, and the resulting solution was filtered, cooled to recrystallize, and vacuum dried for 12 hours, yielding white crystals. A melting point of 113-115°C was measured using a melting point apparatus. Results and Discussion A small spot appeared above spots 1 in both Fig. 1 (thin-layer chromatogram after 30 min) and Fig. 2 (thin-layer chromatogram of mixture after completion of reaction), corresponding to isomers of C-glycosides. Similarly, in Fig. 3 (the thin-layer chromatograms of the first 15 test tubes), for test tubes 7 to 14, the spot above spot 1 also corresponds to the isomers of C-glycosides. Sample II was characterized by FTIR, and the spectrum is shown in Fig. 6. The main absorption peaks are assigned as follows: 3397.2 cm-1 (-OH), 2929.0 cm-1 (-C-H in methyl and methylene groups), 1703.7 cm-1 (C=O), 1423.4 cm-1 (δCH in methylene group), 1361.7 cm-1 (δCH in methine group), 1386.9 cm-1 (δsCH in methyl group), 1084.1 cm-1 (νasC-O-C in ether group), 1044.9 cm-1 (νC-O in R-CH2-OH). � � � 4� 22 15: 26: 37 2013 ( GMT+08: 00) 5. 5 5. 0 4. 5 871. 0 4. 0 885. 0 1557. 9 3. 5 795. 3 1221. 5 1255. 1 %T 3. 0 621. 5 1642. 1 2. 5 559. 8 1361. 7 599. 1 1386. 9 531. 8 1423. 4 2. 0 1008. 4 2929. 0 1. 5 1703. 7 3397. 2 1044. 9 1. 0 0. 5 1084. 1 4000 3000 2000 1000 Wavenumbers ( cm-1) Fig. 6 FTIR spectrum of C-glycosides. The raw material, glucose, was characterized by FTIR, and the spectrum is shown in Fig. 7. The main absorption peaks are assigned as follows: 3391.6 cm-1 (-OH), 3321.65 cm-1 (νOH in -OH), 2943.0 cm-1 (-C-H in methylene and methine groups), 1454.2 cm-1 (δCH in methylene group), 1378.5 cm-1 610 -1 -1 (δCH in methine group), 1145.8 cm (νasC-O-C in ether group), 1103.7 cm (νC-O in R2-CH-OH), -1 1156.1 cm (νC-O in R-CH2-OH). The FTIR spectra of C-glycosides and glucose were compared, as shown in Fig. 8. The comparison indicates that the hydroxyl peak was pronounced in C-glycoside but not present in glucose, indicating that the product of the reaction was C-glycoside. � � � 4� 26 09: 56: 14 2013 ( GMT+08: 00) 4.
Load more

Recommended publications
  • Synthesis and Antimicrobial Evaluation of Some Novel Thiazole, Pyridone, Pyrazole, Chromene, Hydrazone Derivatives Bearing a Biologically Active Sulfonamide Moiety
    Int. J. Mol. Sci. 2014, 15, 1237-1254; doi:10.3390/ijms15011237 OPEN ACCESS International Journal of Molecular Sciences ISSN 1422-0067 www.mdpi.com/journal/ijms Article Synthesis and Antimicrobial Evaluation of Some Novel Thiazole, Pyridone, Pyrazole, Chromene, Hydrazone Derivatives Bearing a Biologically Active Sulfonamide Moiety Elham S. Darwish *, Azza M. Abdel Fattah, Fawzy A. Attaby and Oqba N. Al-Shayea Department of Chemistry, Faculty of Science, Cairo University, Giza 12613, Egypt; E-Mails: [email protected] (A.M.A.F.); [email protected] (F.A.A.); [email protected] (O.N.A.-S.) * Author to whom correspondence should be addressed; E-Mail: [email protected]; Tel.: +20-100-588-1771; Fax: +202-570-8480. Received: 10 November 2013; in revised form: 10 January 2014 / Accepted: 13 January 2014 / Published: 17 January 2014 Abstract: This study aimed for the synthesis of new heterocyclic compounds incorporating sulfamoyl moiety suitable for use as antimicrobial agents via a versatile, readily accessible N-[4-(aminosulfonyl)phenyl]-2-cyanoacetamide (3). The 2-pyridone derivatives were obtained via reaction of cyanoacetamide with acetylacetone or arylidenes malononitrile. Cycloaddition reaction of cyanoacetamide with salicyaldehyde furnished chromene derivatives. Diazotization of 3 with the desired diazonium chloride gave the hydrazone derivatives 13a–e. Also, the reactivity of the hydrazone towards hydrazine hydrate to give Pyrazole derivatives was studied. In addition, treatment of 3 with elemental sulfur and phenyl isothiocyanate or malononitrile furnished thiazole and thiophene derivatives respectively. Reaction of 3 with phenyl isothiocyanate and KOH in DMF afforded the intermediate salt 17 which reacted in situ with 3-(2-bromoacetyl)-2H-chromen-2-one and methyl iodide afforded the thiazole and ketene N,S-acetal derivatives respectively.
    [Show full text]
  • Feiii, Cuii and Znii Complexes of the Rigid 9-Oxido-Phenalenone Ligand—Spectroscopy, Electrochemistry, and Cytotoxic Properties
    International Journal of Molecular Sciences Article FeIII, CuII and ZnII Complexes of the Rigid 9-Oxido-phenalenone Ligand—Spectroscopy, Electrochemistry, and Cytotoxic Properties Katharina Butsch 1, Alexander Haseloer 1 , Simon Schmitz 1, Ingo Ott 2, Julia Schur 2 and Axel Klein 1,* 1 Department für Chemie, Institut für Anorganische Chemie, Universität zu Köln, Greinstraße 6, D-50939 Köln, Germany; [email protected] (K.B.); [email protected] (A.H.); [email protected] (S.S.) 2 Institute of Medicinal and Pharmaceutical Chemistry, Technische Universität Braunschweig, Beethovenstrasse 55, D-38106 Braunschweig, Germany; [email protected] (I.O.); [email protected] (J.S.) * Correspondence: [email protected] Abstract: The three complexes [Fe(opo)3], [Cu(opo)2], and [Zn(opo)2] containing the non-innocent anionic ligand opo− (opo− = 9-oxido-phenalenone, Hopo = 9-hydroxyphenalonone) were synthe- 1 sised from the corresponding acetylacetonates. [Zn(opo)2] was characterised using H nuclear magnetic resonance (NMR) spectroscopy, the paramagnetic [Fe(opo)3] and [Cu(opo)2] by electron paramagnetic resonance (EPR) spectroscopy. While the EPR spectra of [Cu(opo)2] and [Cu(acac)2] in dimethylformamide (DMF) solution are very similar, a rather narrow spectrum was observed for [Fe(opo)3] in tetrahydrofuran (THF) solution in contrast to the very broad spectrum of [Fe(acac)3] in − Citation: Butsch, K.; Haseloer, A.; THF (Hacac = acetylacetone, 2,4-pentanedione; acac = acetylacetonate). The narrow, completely Schmitz, S.; Ott, I.; Schur, J.; Klein, A. isotropic signal of [Fe(opo)3] disagrees with a metal-centred S = 5/2 spin system that is observed FeIII, CuII and ZnII Complexes of the in the solid state.
    [Show full text]
  • Glycosyl Barbiturate Ligands of Bacterial Lectins: from Monomer Design to Glycoclusters and Glycopolymers François Portier, Anne Imberty, Sami Halila
    View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by Archive Ouverte en Sciences de l'Information et de la Communication Expeditious Synthesis of C -Glycosyl Barbiturate Ligands of Bacterial Lectins: From Monomer Design to Glycoclusters and Glycopolymers François Portier, Anne Imberty, Sami Halila To cite this version: François Portier, Anne Imberty, Sami Halila. Expeditious Synthesis of C -Glycosyl Barbiturate Lig- ands of Bacterial Lectins: From Monomer Design to Glycoclusters and Glycopolymers. Bioconjugate Chemistry, American Chemical Society, 2019, 30 (3), pp.647-656. 10.1021/acs.bioconjchem.8b00847. hal-02322076 HAL Id: hal-02322076 https://hal.archives-ouvertes.fr/hal-02322076 Submitted on 4 Aug 2020 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. EXPEDITIOUS SYNTHESIS OF C‐GLYCOSYL BARBITURATE LIGANDS OF BACTERIAL LECTINS: FROM MONOMER DESIGN TO GLYCOCLUSTERS AND GLYCOPOLYMERS François Portier, Anne Imberty and Sami Halila* Univ. Grenoble Alpes, CNRS, CERMAV, 38000 Grenoble, France. E‐mail: [email protected]; Fax: +33 4 76 54 72 03; Tel : +33 4 76 03 76 66 ABSTRACT The approach developed here offers a straightforward and efficient access to ‐C‐glycosyl barbiturates ligands, spanning from glycomimetics to multivalent C‐neoglycoconjugates, with the aim of deciphering structural parameters impacting the binding to pathogenic lectins.
    [Show full text]
  • Effect of the Titanium Isopropoxide:Acetylacetone Molar Ratio on the Photocatalytic Activity of Tio2 Thin Films
    molecules Article Effect of the Titanium Isopropoxide:Acetylacetone Molar Ratio on the Photocatalytic Activity of TiO2 Thin Films Jekaterina Spiridonova 1,* , Atanas Katerski 1, Mati Danilson 2 , Marina Krichevskaya 3,* , Malle Krunks 1 and Ilona Oja Acik 1,* 1 Laboratory of Thin Films Chemical Technologies, Department of Materials and Environmental Technology, Tallinn University of Technology, Ehitajate tee 5, 19086 Tallinn, Estonia; [email protected] (A.K.); [email protected] (M.K.) 2 Laboratory of Optoelectronic Materials Physics, Department of Materials and Environmental Technology, Tallinn University of Technology, Ehitajate tee 5, 19086 Tallinn, Estonia; [email protected] 3 Laboratory of Environmental Technology, Department of Materials and Environmental Technology, Tallinn University of Technology, Ehitajate tee 5, 19086 Tallinn, Estonia * Correspondence: [email protected] (J.S.); [email protected] (M.K.); [email protected] (I.O.A.); Tel.: +372-620-3369 (I.O.A.) Academic Editors: Smagul Karazhanov, Ana Cremades and Cuong Ton-That Received: 31 October 2019; Accepted: 25 November 2019; Published: 27 November 2019 Abstract: TiO2 thin films with different titanium isopropoxide (TTIP):acetylacetone (AcacH) molar ratios in solution were prepared by the chemical spray pyrolysis method. The TTIP:AcacH molar ratio in spray solution varied from 1:3 to 1:20. TiO2 films were deposited onto the glass substrates at 350 ◦C and heat-treated at 500 ◦C. The morphology, structure, surface chemical composition, and photocatalytic activity of the obtained TiO2 films were investigated. TiO2 films showed a transparency of ca 80% in the visible spectral region and a band gap of ca 3.4 eV irrespective of the TTIP:AcacH molar ratio in the spray solution.
    [Show full text]
  • Synthesis and Characterization of Schiff Bases Derived from Acetylacetone and Their Theoretical Study
    International Journal of ChemTech Research CODEN( USA): IJCRGG ISSN : 0974-4290 Vol.5, No.1, pp 204-211, Jan-Mar 2013 Synthesis And Characterization Of Schiff Bases Derived From Acetylacetone And Their Theoretical Study Adnan dib Department of Chemistry, Faculty of Science, Laboratory of Organic Chemistry, University of Damascus, Syria Corres.author: [email protected] Abstract: Schiff basesderived from acetylacetone were synthesized and characterized by Ms, IR, 1H ,13C NMR and element analysis. Hyper Chem-6 program has been used to predict structural geometries of compounds in gas phase. The heat of formation (ΔHf º) and binding energy (ΔEb) at 298 ºK for the free ligand was calculated by PM3 method. Keywords: Schiff bases, acetylacetone, hydrazine, PM3 method. Introduction Experimental Schiff bases are one of the most versatile classes of Reagents and Apparatus. ligands for the study of the coordination of transition All the chemicals used were of AnalaR grade and metals[1]. Their ease of synthesis (by the procured from Sigma-Aldrich and Fluka. Metal salts condensation of an aldehyde/ketone with an amine), were purchased from E. Merck and were used as multidenticity (from mono to hexadentate), received. Distilled water was used in extraction combination of donor atoms (coordination usually experimentals. The solvents were saturated with through the imine nitrogen and other atoms like each other before use in order to prevent volume oxygen, sulfur or nitrogen) and stability have made changes of the phases during extraction. The C, H, them the preferred ligand system in catalysis, and N were analyzed on a Carlo-Erba 1106 biological modeling, the design of molecular elemental analyzer.
    [Show full text]
  • Determination of Solvent Effects on Ketoðenol Equilibria of 1,3-Dicarbonyl Compounds Using NMR: Revisiting a Classic Physical C
    In the Laboratory Determination of Solvent Effects on Keto–Enol Equilibria W of 1,3-Dicarbonyl Compounds Using NMR Revisiting a Classic Physical Chemistry Experiment Gilbert Cook* and Paul M. Feltman Department of Chemistry, Valparaiso University, Valparaiso, IN 46383; *[email protected] “The influence of solvents on chemical equilibria was discovered in 1896, simultaneously with the discovery of keto–enol tautomerism in 1,3-dicarbonyl compounds” (1). The solvents were divided into two groups according to their ability to isomerize compounds. The study of the keto–enol tautomerism of β-diketones and β-ketoesters in a variety of solvents using proton NMR has been utilized as a physical Figure 1. The β-dicarbonyl compounds studied in the experiment. chemistry experiment for many years (2, 3). The first reported use of NMR keto–enol equilibria determination was by Reeves (4). This technique has been described in detail in an experiment by Garland, Nibler, and Shoemaker (2). panded (i) to give an in-depth analysis of factors influencing The most commonly used β-diketone for these experi- solvent effects in tautomeric equilibria and (ii) to illustrate ments is acetylacetone (Scheme I). Use of proton NMR is a the use of molecular modeling in determining the origin of viable method for measuring this equilibrium because the a molecule’s polarity. The experiment’s original benefits of tautomeric keto–enol equilibrium is slow on the NMR time using proton NMR as a noninvasive method of evaluating scale, but enol (2a)–enol (2b) tautomerism is fast on this scale equilibrium are maintained. (5). It has been observed that acyclic β-diketones and β- Experimental Procedure ketoesters follow Meyer’s rule of a shift in the tautomeric equi- librium toward the keto tautomer with increasing solvent Observations of the solvent effects for three other 1,3- polarity (6).
    [Show full text]
  • Acetylacetone
    Safety data sheet acc. to Safe Work Australia - Code of Practice Acetylacetone ≥98 %, for synthesis article number: 6716 date of compilation: 2016-11-08 Version: GHS 2.0 en Revision: 2021-06-11 Replaces version of: 2016-11-08 Version: (GHS 1) SECTION 1: Identification of the substance/mixture and of the company/ undertaking 1.1 Product identifier Identification of the substance Acetylacetone ≥98 %, for synthesis Article number 6716 CAS number 123-54-6 Alternative name(s) Pentane-2,4-dione 1.2 Relevant identified uses of the substance or mixture and uses advised against Relevant identified uses: Laboratory chemical Laboratory and analytical use Uses advised against: Do not use for products which come into contact with foodstuffs. Do not use for private purposes (household). 1.3 Details of the supplier of the safety data sheet Carl Roth GmbH + Co KG Schoemperlenstr. 3-5 D-76185 Karlsruhe Germany Telephone:+49 (0) 721 - 56 06 0 Telefax: +49 (0) 721 - 56 06 149 e-mail: [email protected] Website: www.carlroth.de Competent person responsible for the safety data :Department Health, Safety and Environment sheet: e-mail (competent person): [email protected] 1.4 Emergency telephone number Name Street Postal Telephone Website code/city NSW Poisons Information Centre Hawkesbury Road 2145 West- 131126 Childrens Hospital mead, NSW SECTION 2: Hazards identification 2.1 Classification of the substance or mixture Classification acc. to GHS Section Hazard class Cat- Hazard class and Hazard egory category statement 2.6 Flammable liquid 3 Flam. Liq. 3 H226 3.1O Acute toxicity (oral) 4 Acute Tox.
    [Show full text]
  • Polarography As a Measure of Ionic Environment
    University of the Pacific Scholarly Commons University of the Pacific Theses and Dissertations Graduate School 1965 Polarography As A Measure Of Ionic Environment James Wilburne Larsen University of the Pacific Follow this and additional works at: https://scholarlycommons.pacific.edu/uop_etds Part of the Chemistry Commons Recommended Citation Larsen, James Wilburne. (1965). Polarography As A Measure Of Ionic Environment. University of the Pacific, Dissertation. https://scholarlycommons.pacific.edu/uop_etds/2881 This Dissertation is brought to you for free and open access by the Graduate School at Scholarly Commons. It has been accepted for inclusion in University of the Pacific Theses and Dissertations by an authorized administrator of Scholarly Commons. For more information, please contact [email protected]. .. i:' ~)~-~;~::"',:'.,·~-~ -~·-:.·: ~ -~ ·. ,. '~:-··~· ··:.\';~<_; i ~~ .:•i'{O" .1"' POLAROGRAPHY AS A MEASURE OF IONIC ENVIRONMENT A Dissertation _Presented to the Faculty of the Graduate School University of the Pacific In Partial Fulfillment of the Requirements for the Degree (f ' Doctor of Philosophy by James Wilburne Larsen June 1965 This disseljtatic;m,, written apd submitted by is approved for recornrnendat,ipn to the Graduate Co~ncil, University of th~ P~(::.ific • . D~partmept Chairwan or Dean: ACKNOWLEDGEMENTS The writer wishes to express his appreciation to the faculty of the Chemistry Department for their assistance, especially Dr. Herschel Frye for his criticisms and guidance. TABLE OF CONTENTS CHAPTER PAGE I. INTRODUCTION
    [Show full text]
  • Biosynthesis of Acetylacetone Inspired by Its Biodegradation
    Zhou et al. Biotechnol Biofuels (2020) 13:88 https://doi.org/10.1186/s13068-020-01725-9 Biotechnology for Biofuels RESEARCH Open Access Biosynthesis of acetylacetone inspired by its biodegradation Yifei Zhou1,2, Yamei Ding3, Wenjie Gao1, Jichao Wang1, Xiutao Liu1,2, Mo Xian1, Xinjun Feng1* and Guang Zhao1,4* Abstract Background: Acetylacetone is a commercially bulk chemical with diverse applications. However, the traditional manufacturing methods sufer from many drawbacks such as multiple steps, harsh conditions, low yield, and environ- mental problems, which hamper further applications of petrochemical-based acetylacetone. Compared to conven- tional chemical methods, biosynthetic methods possess advantages such as being eco-friendly, and having mild conditions, high selectivity and low potential costs. It is urgent to develop biosynthetic route for acetylacetone to avoid the present problems. Results: The biosynthetic pathway of acetylacetone was constructed by reversing its biodegradation route, and the acetylacetone was successfully produced by engineered Escherichia coli (E. coli) by overexpression of acetylac- etone-cleaving enzyme (Dke1) from Acinetobacter johnsonii. Several promising amino acid residues were selected for enzyme improvement based on sequence alignment and structure analysis, and the acetylacetone production was improved by site-directed mutagenesis of Dke1. The double-mutant (K15Q/A60D) strain presented the highest acetylacetone-producing capacity which is 3.6-fold higher than that of the wild-type protein. Finally, the strain accu- mulated 556.3 15.2 mg/L acetylacetone in fed-batch fermentation under anaerobic conditions. ± Conclusions: This study presents the frst intuitive biosynthetic pathway for acetylacetone inspired by its biodegra- dation, and shows the potential for large-scale production.
    [Show full text]
  • Physical Chemical Studies on Inorganic Coordination Compounds. I. Metallic Complexes of Dimethylsulfoxide. II. Preparation and Spectral Studies of Vanadyl Complexes
    Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1961 Physical Chemical Studies on Inorganic Coordination Compounds. I. Metallic Complexes of Dimethylsulfoxide. II. Preparation and Spectral Studies of Vanadyl Complexes. Lawrence Henry Holmes Jr Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Holmes, Lawrence Henry Jr, "Physical Chemical Studies on Inorganic Coordination Compounds. I. Metallic Complexes of Dimethylsulfoxide. II. Preparation and Spectral Studies of Vanadyl Complexes." (1961). LSU Historical Dissertations and Theses. 713. https://digitalcommons.lsu.edu/gradschool_disstheses/713 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Historical Dissertations and Theses by an authorized administrator of LSU Digital Commons. For more information, please contact [email protected]. This dissertation has been 62-1233 microfilmed exactly as received H O L M E S , Jr., Lawrence Henry, 1935- PHYSICAL CHEMICAL STUDIES ON INORGANIC COORDINATION COMPOUNDS. I. METALLIC COMPLEXES OF DIMETHYLSULFOXIDE. II. PRE­ PARATION AND SPECTRAL STUDIES OF VANA­ DYL COMPLEXES. University Microfilms, Inc., Ann Arbor, Michigan H O L M E S , Jr., Lawrence Henry, 193 5- 62-1233 Louisiana State University, Ph.D., 1961 Chemistry, inorganic University Microfilms, Inc., Ann Arbor, Michigan PHYSICAL' CHEMICAL STUDIES ON INORGANIC COORDINATION COMPOUNDS I. METALLIC COMPLEXES OF DIMETHYIBULFOXIDE II. PREPARATION AND SPECTRAL STUDIES OF VANADYL COMPLEXES A DISSERTATION Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Ffechanical College in partial fulfillment of the requirements for the degree of Doctor of Philosophy in The Department of Chemistry by Lawrence Henry Holmes, Jr.
    [Show full text]
  • Preparation of Acetylacetone Using Sodium Alkoxide and Dispersed Sodium As Catalysts
    K. K. GEORGIEFF I Research Laboratories, Shawinigan Chemicals, Ltd., Shawinigan Falls, Quebec, Canada Preparation of Acetylacetone Using Sodium Alkoxide and Dispersed Sodium as Catalysts Reduction in costs, hazards, and time of re- action makes this process commercially attractive 1NDUSTRIAL production of acetylacetone ester, length of time required to complete The yields with methyl acetone, which by the Claisen condensation of acetone the reaction, and effect of temperature on had been dried with acetic anhydride, and aliphatic acetate esters, using sodium yield are lacking. This information is were identical to those obtained with or sodium alkoxide as catalyst, has been given in the present article. The amount chemically pure synthetic mixtures of the made economically impossible by the of by-product acetoacetic ester produced same composition. hazards of the reaction, the low yields, in the author’s experiments was small as The inert diluent materially affected and the great length of time required compared to that divulged in the patent. the yield, but the amount was not crit- for reaction of the last few per cent of the This was probably due to a difference in ical within wide ranges of concentra- sodium, because of coating of the par- the amount of diluent used, although the tion. Best results were obtained with ticles. The latter disadvantage has, to a slightly different order of adding the re- medium boiling hydrocarbons such as small extent, been alleviated by use of so- agents may have had a minor effect. toluene. Isohexane gave somewhat called “sodium sand.” Within recent lower yields, while Varsol (a commercial years, dispersed sodium of 1- to 20- petroleum fraction, boiling point 154’ micron particle size has become commer- Sodium Alkoxide as Catalyst to 175’ C.) gave much poorer results.
    [Show full text]
  • Design, Synthesis and Docking Studies of Novel Thiazole Derivatives Incorporating Pyridine Moiety and Assessment As Antimicrobial Agents Rizk E
    www.nature.com/scientificreports OPEN Design, synthesis and docking studies of novel thiazole derivatives incorporating pyridine moiety and assessment as antimicrobial agents Rizk E. Khidre 1,2,3* & Ibrahim Ali M. Radini1,3 A novel series of substituted 4,6-dimethyl-2-oxo-1-(thiazol-2-ylamino)-1,2-dihydropyridine- 3-carbonitrile derivatives 6, 9, 13, 15, and 17 was synthesized in a good to excellent yield from the reaction of 1-(3-cyano-4,6-dimethyl-2-oxopyridin-1(2H)-yl)thiourea with 2-oxo-N’- arylpropanehydrazonoyl chloride, chloroacetone, α-bromoketones, ethyl chloroacetate, and 2,3-dichloroquinoxaline, respectively. The potential DNA gyrase inhibitory activity was examined using in silico molecular docking simulation. The novel thiazoles exhibit dock score values between − 6.4 and − 9.2 kcal/mol and they were screened for their antimicrobial activities. Compound 13a shown good antibacterial activities with MIC ranged from 93.7–46.9 μg/mL, in addition, it shown good antifungal activities with MIC ranged from 7.8 and 5.8 μg/mL. Tiazoles are present in numerous natural products e.g. epithilone, thiostrepton, thiamine pyrophosphate (TPP), carboxylase vitamin B1, and penicillin1. Tiazoles have diverse applications in drug development for treatment allergies2, infammation3, HIV infections4, hypertension5, bacterial infections 6, hypnotics7, schizophrenia8, and pain9, as novel inhibitors of bacterial DNA gyrase B10, and as fbrinogen receptor antagonists with antithrom- botic activity11. Tey exhibited fabulous pharmaceutical activities for instance antifungal 12, antimicrobial13–15, anti-infammatory16,17, analgesic18, and anti-cancer19,20, anticonvulsant activities 21. Tere are several commercial drugs contain thiazole moiety (Fig. 1). Pyridines are an important class of heterocyclic compounds because they occur in many natural compounds that have biological activity such as vitamin B3 (niacin) and vitamin B6 (pyridoxin) and natural alkaloids 22.
    [Show full text]